Polyoxyalkylated alkyl phenol-formal-dehyde-alkylene polyamine resins



United States Patent 8 Claims. (Cl. 260-338) This application isadivision of our copending application Serial No. 65,564, filed October28, 1960, now US. Patent No. 3,166,516 which in turn is acontinuation-inpart of our now abandoned application Serial No. 635,-579, filed January 23, 1957.

This application relates to new and useful polyoxyalkylated resinshaving surface-active properties. The polyoxyalkylated resins are usefulin the treatment of emulsions of mineral oil and water, especiallywater-inoil emulsions, for the purpose of breaking the emulsions andseparating the oil and water.

The compositions of the invention may be used to treat emulsions such aspetroleum emulsions commonly encountered in the production, handling andrefining of crude mineral oil, for the purpose of separating the oilfrom the Water. Also, the compositions may be used in the treatment ofother water-in-oil type of emulsions wherein the emulsions are producedartificially or naturally and the resolution of the emulsions presents aproblem of recovery of disposal. A particularly important aspect of theinvention .is concerned with the beneficial properties of thecompositions of the invention in desalting.

Petroleum emulsions are, in general, of the water-inoil type wherein theoil acts as a continuous phase for the dispersal of finely-dividedparticles of naturally occurring waters or brines. These emulsions areoften extremely stable and will not resolve on long standing. It is tobe understood that water-in-oil emulsions may occur artificiallyresulting from any one or more of numerous operations encountered invarious industries. The emulsions obtained from producing Wells and fromthe bottom of crude oil storage tanks are commonly referred to as cutoil, emulsified oil, bottom settlings, and BS.

One type of process involves subjecting an emulsion of the water-in-oiltype to the action of a deemulsifying agent of the kind hereinafterdescribed, thereby causing the emulsion to resolve and stratify into itscomponent parts of oil and water or brine after the emulsion has beenallowed to stand in a relatively quiescent state.

Still another type of process involves the use of a deemulsifying agentof the kind hereinafter described in refinery desalting operations. Inthe refining of many crude oils a desalting operation is necessary inorder to prevent the accumulation of large deposits of salt in thestills and to prevent corrosion resulting from the decomposition of suchsalts under high still temperatures. In a typical desalting installationto 10% of fresh water is added to the crude oil charge stock andemulsified therein by means of a pump or through a differential pressurevalve. A deemulsifying agent is added and the treated oil permitted tostand in a quiescent state for relatively short periods of time allowingthe salt-laden water to stratify, whereupon it is bled off to wasteresulting in 90% to 98% removal of salt content. This operation iscarried out continuously as contrasted with batch treating.

In desalting operations where petroleum emulsions are createdartificially and then broken, the conditions 3,278,037 Patented Oct. 11,1966 employed are usually quite different from those used in breakingwater-in-oil petroleum emulsions at the well. The temperature may rangefrom F. to 350 F. and are preferably around F. to 210 F. The pressuresare those which are developed by heating under autogenous pressures andmay be, for example 215 to 250 pounds per square inch gauge. The time ofheating .is subject to variation but is usually around 15 to 30 minutes.Since a refinery unit may handle up to 50,000 barrels of oil per day andthe amount of salt present may be, for example, 15 pounds to 250 poundsof salt per thousand barrels of oil, it will be appreciated that theseparation of this salt is very important, especially since" it isusually desired to reduce the salt content of the oil by at least 90%.

One of the objects of the present invention is to provide new and usefulcompositions of matter which are water-wettable, interfacial andsurface-active in order to enable their use as deemulsifiers or for suchuses where surface-active characteristics are necessary or desirable.

Another object is to provide surface-active, polyoxyalkylated resinsuseful is resolving petroleum oil emulsions, especially water-in-oilemulsions.

An additional object of the invention is to provide surface-active,polyoxyalkylated resins especially useful for desalting petroleum oils.Other objects will appear hereinafter.

In accordance with the invention, the crude oil deemulsifying agents areoxylakylated condensation products obtained by reacting phenols whichare primarily difunctional, alkyl phenols, the alkyl groups having anaver-age of 415 carbons, formaldehyde, and alkylene polyamides. Ortho,orthoor para, ortho-dialkyl phenols are not suitable for compositions ofthis invention, but amounts up to 25% of said dialkyl phenols in thedifunctional, alkyl phenol reactant may be tolerated. Dialkyl phenolswith one alkyl group in the orthoor para-position and one alkyl group inthe meta-position are difunctional phenols for the purposes of thisinvention. The term difunctional phenol relates to the methylol-formingreactivity of the phenol with formaldehyde.

The preferred alkylene polyamines are those having two primary aminogroups, e.g., ethylene diamine, propylene diamine, hexamethylenediamine, diethylene triamine, triethylene tetramine, tetraethylenepentamine, higher polyalkylene polyamine homologs thereof up to about 10amino groups per molecule, mixtures thereof, and the corresponding 1,2-and 1,3-polypropylene polyamines.

The preferred phenols used in the condensate polymers are monoalkylphenols having the alkyl group in the functional positions of thephenolic ring upon which methylol groups form in the reaction withfonmaldehyde, i.e., the orthoor para-positions. The alkyl groups in thephenolic substituent may be the same or they may be different, as when amixture of alkyl phenols is the phenolic reactant. The average number ofcarbons in the alkyl groups of the phenolic reactant should be in therange of about 4-15. Alkyl groups of 4-9 carbons are preferred.

Examples of such phenols are o-butyl phenol, o-isobutyl phenol,p-n-butyl phenol, p-isobutyl phenol, p-tert. butyl phenol, o-amylphenol, p-amyl phenol, p-tert. amyl phenol, o-octyl phenol, p-octylphenol, o-nonyl phenol, p-nonyl phenol, o-dodecyl phenol, p-dodecylphenol, mixtures of o-phenols and p-alkyl phenols, mixtures of ortho orpara alkyl phenols with up to 25% o-, p-dialkyl phenols with 4-15carbons in the alkyl groups such as the commercially available mixtureof about 90% p-nonyl phenol with about 10% 0-, p-dinonyl phenol, andmixtures of difunctional monoalkyl phenols whose alkyl groups average atleast about 4 carbons and not more than about 15 carbons, e.g., mixturesof p-octyl phenol 9 and p-nonyl phenol, a mixture of about 30%p-isopropyl phenol and 70% p-octyl phenol, and the like.

The oxyalkylating agents are lower alkylene oxides, e.g., ethyleneoxide, 1,2-propylene oxide, or mixtures of ethylene oxide and1,2-propylene oxide and the weight ratio of the alkylene oxide to thephenol-formaldehydepolyamine condensation product will, for mostapplications, fall between about 2:3 and 10:1, or even higher,respectively. The phenol-frmaldehyde-polyamine condensation productscontain about 4 to 15 phenolic nuclei per resin molecule.

Where both ethylene oxide and propylene oxide are used to oxyalkylatethe condensation product, they may be reacted as a mixture or the oxidemay be added se quentiallye.g., the propylene oxide being added to theresin first and the ethylene oxide being added to the oxypropylene-1,2groups. In the latter case, the terminal oxyalkylate groups are those ofoxyethylene, which have primary hydroxyl groups. Simultaneous reactionof a mixture of the oxides probably gives an oxyalkylated product havingboth types of terminal hydroxy groups,

and

CH (IJHC H;

Phenol-formaldehyde-polyamine condensation Thephenol-formaldehyde-alkylene polyamine condensation products areprepared by reacting formaldehyde or a substance which breaks down toformaldehyde under reaction conditions, e.g., paraformaldehyde ortrioxane, the difunctional alkyl phenol, often preferably a crudemixture of alkylated phenols for economic reasons, and the alkylenepolyamine by heating the reactants in the presence of a small amount ofan alkaline catalyst such as sodium hydroxide under the reactiontemperatures and conditions causing the elimination of water ofreaction. The condensates are phenolic and alkylene polyamine residuesconnected by methylene bridges. In some cases, the polyamine itselfserves as the alkaline catalyst.

The condensation reaction preferably is carried out under substantiallyanhydrous conditionsexcepting the water produced during the reaction.The aqueous distillate which begins to form when the reactants areheated is collected and removed [from the reaction mixture.

The phenol-formaldehyde-polyamine condensation product may be preparedby agitating and heating a mixture of the three reactants. In this case,the presence of the polyamine provides sufficient alkalinity for thecondensation reaction. Alternatively, the alkyl phenol and formaldehydemay be only partially condensed e.g., by heating these reactants abovefor a shorter period of time than necessary to obtain completecondensation and leaving in the reaction mixture some unreacted phenoland formaldehyde. The reaction mixture is then cooled somewhat, and thealkylene polyamine is added to the reaction mixture. Heat is againapplied to remove the water of reaction. Heating is continued until theamount of aqueous distillate collected indicates that the condensationis complete. Alternatively, the alkyl phenol may be precondensed with aportion of the formaldehyde in the form of precursor phenol-formaldehydeintermediate condensate. The intermediate condensate is thereafterfurther condensed by reacting it with the remainder of the formaldehydeand the alkylene polyamine thereafter added to the precursor condensate.

This aspect of the invention is illustrated in the following examples,but is not limited thereto.

EXAMPLE A In a three-necked reaction flask provided with means ofmechanical stirring and a return condenser system permitting the removalof any aqueous phase formed in the course of the reaction, there isadded 750 parts of a crude alkylate phenol which comprises anundistilled p-nonylphenol containing approximately 10% of o,p-dinonylphenol, parts paraformaldehyde and 2 parts of finely divided sodiumhydroxide which is present as a catalyst in the reaction. Thesematerials are heated to 60 C., and at this point the source of heat isremoved. The temperature rises slowly to approximately C., at whichpoint it is held for two hours. At this point 250 parts of a suitablehydrocarbon extract is added, and heat is ap plied to remove 36 parts ofaqueous distillate at a maximum temperature of 150 C. The reaction massis cooled to C., and at this point is added 100 parts of a crude mixtureof polyethylene polyamines, approximately 10% of which istriethylenetetramine, 40% tetraethylenepentamine and the remainderhomologs higher than tetra ethylene pentamine. Heat is again applied toremove 22 parts of aqueous distillate with a maximum final temperatureof 220 C. At this point the material is cooled to 150 C., and 250 partsof a suitable hydrocarbon extract is added to give the finishedphenol-formaldehydealkylene polyamine resin.

EXAMPLE B In a manner similar to Example A, 750 parts of the same crudealkylate phenol, 110 parts paraformaldehyde and 2 parts sodium hydroxidewere heated for 2 hours at temperatures in the range of 100l10 C. Afterthis period of heating, 250 parts of a suitable hydrocarbon extract wereadded, and 36 parts of aqueous distillate were removed with a maximumfinal temperature of C. The reaction mass was then cooled to 90 C., and50 parts of diethylenetriamine were added. The material Was again heatedto remove an additional 32 parts of aqueous distillate with a maximumfinal tempearture of 210 C. The material was cooled to C., and 250 partsof a suitable hydrocarbon extract were added to give the finished resin.

EXAMPLE C In a manner similar to Example A, 750 parts of the same crudealkylate phenol, 120 parts of paraformaldehyde and 2 parts sodiumhydroxide were reacted for a period of 2 hours at temperatures between100-110 C. After this period of heating, 250 parts of a suitablehydrocarbon extract were added and the temperature raised to remove 36parts of aqueous distillate with a maximum temperature of 136 C. Thematerial was cooled to 100 C., and at this point 60 parts of the crudemixture of higher polyethylene polyamines, as described in Example A,were added. The reaction mass was again further heated to remove anadditional 36 /2 parts of aqueous distillate with a maximum finaltemperature of 212 C. The material was then cooled to 150 C., and 250parts of a suitable hydrocarbon extract were added to give the finishedresin.

EXAMPLE D In a manner similar to Example A, 3750 parts of crude alkylatephenol, 700 parts paraformaldehyde and 20 parts sodium hydroxide werereacted at temperatures between 100-110 C. for a period of 2 hours. Atthe end of this period of heating 2000 parts of a suitable hydrocarbonextract were added, and the temperature was raised to remove 200 partsof aqueous distillate with a maximum final temperature of 116 C. At thispoint, 1000 parts of a suitable hydrocarbon extract, and 350 partsdiethylene triamine were added. The temperature is again raised toremove 255 parts aqueous distillate with a maximum final temperature of210 C. This gives the finished resin.

EXAMPLE E In a three-necked reaction flask provided with means ofmechanical stirring and a return condenser system permitting the removalof any aqueous phase formed in the course of reaction, there is added500 parts of the crude :alkylate phenol, as described in IntermediateExample A, and 70 parts of diethylenetriamine. These materials areheated together to approximately 60 C. at which point the addition ofparaformaldehyde is begun. Then 108 parts paraformaldehyde are addedslowly and in portions in such a manner to maintain the temperature ofthe reaction mass below 90 C. After the addition of the paraformaldehydehas been completed, 200 parts of a suitable hydrocarbon extract areadded and the temperature raised to remove aqueous distillate in theamount of 55 parts with a maximum final temperature of 200 C. This givesthe finished phenol-formaldehyde-alkylene polyamine resin.

The ratio of amine to phenol in the above example is calculated to giveabout one basic nitrogen per mole of phenol. It should be further notedin this example that the amine ope-rates as a reactive catalyst, or inother words, no sodium hydroxide or other alkaline material is used as acatalyst.

EXAMPLE F In a manner similar to Example E, 500 parts of the crudealkylate phenol and 103 parts of diethylenetriamine are reacted with 120parts of paraformaldehyde. After the addition of the paraformaldehyde iscompleted, 200 parts of a suitable hydrocarbon extract are added and thetemperature raised to remove 69 parts of aqueous distillate with amaximum final temperature of 176 C. This gives the finished resin.

In the above example it might be noted that the ratio of amine to phenolprovides about one primary amino group per mole of phenol. Also, as inExample E, the amine functions as a reactive catalyst.

The alkylene polyamine serves as a linking radical in the polymer chain,connected at two amino nitrogens by a methylene group, supplied by theformaldehyde to the phenolic nuclei and possibly partly to otheralkylene polyamine groups. With alkylene polyamines containing twoterminal primary amino groups, such as those heretofore named, thereaction with formaldehyde in all probability is at the terminal primaryamino groups.

The ratio of the phenol to the alkylene polyamine in the polymercondensate ranges from about 1:1 to about 1, respectively, and the molarquantity of the reacted aldehyde is in the range of about 0.9 to about1.5 times the total reacted mols of the phenol and the alkylenepolyamine. With polyamines containing only 2,3, or 4 amino groups, themol ratio of phenol to polyamine preferably ranges from about 1:1 to4:1, respectively. At least some phenol and polyamine residues in all ofthe various types of condensates will be linked by the characteristic.group.

wherein R is the alkyl group in the oor p-position, the methylene bridgeis in the oor pposition, and R is the remainder of the polyamineresidue. Some of the polymeric condensates will have at least one of thefollowing linking groups.

( (I H (I) H (b) R NHCH NHR wherein the methylene bridge in (a) and Rand R are as above described. In all of the condensates, at least aportion of the alkylene polyamine residues are chemically combinedinternally in the structure of the phenolformaldehyde-alkylene polyamineresins.

Oxyalkylation of the condensation products Having prepared theintermediate phenol-formaldehyde-polyamine condensation products, thenext step is the oxyalkylation of the condensation product. This isachieved by mixing the intermediate phenol-formaldehyde-polyaminecondensation product in a hydrocarbon solvent with a small amount ofsodium or potassium hydroxide in an autoclave. The condensation productis heated above 100 C., and preferably not over 180 C., and the alkyleneoxide is charged into the autoclave until the pressure is in thevicinity of 75 to 100 p.s.i.

The reaction mixture is gradually heated until an exothermic reactionbegins. The external heating is then removed, and alkylene oxide isadded at such a rate that the temperature is maintained between about150160 C. in a pressure range of to p.s.i. After all of the alkyleneoxide has been added, the temperature is maintained for an additional 10to 20 minutes to assure substantially complete reaction of the alkyleneoxide. The resulting product is the alkylene oxide adduct of an alkylphenol-formaldehyde-polyamine condensation prodnot, in which the weightratio of the oxide to the condensation product is between about 2:3 and10:1, respectively, or even slightly higher.

Some preferred embodiments of the oxyalkylated, alkylphenol-formaldehyde-polyamine condensation products and methods of theirpreparation are illustrated in the following examples wherein all partsare by weight unless otherwise stated, but the invention is not limitedthereto.

EXAMPLE I In an autoclave having a nominal capacity of 5 gallons,equipped with a means of external heating, cooling and mechanicalagitation, there is charged 22 parts of the resin of Example D. Into atransfer bomb there is charged 25 parts ethylene oxide. The reactantsare heated to C., and the ethylene oxide is added until the reactorpressure is 30 p.s.i. The reaction mixture is gradually heated until anexothermic reaction begins to take place. The external heating is thenremoved, and ethylene oxide is added at such a rate that the temperatureis maintained between 160 C. with a pressure range of 80 to 100 p.s.i.After approximately two hours, 22 parts of ethylene oxide has been addedto the autoclave, and the temperature is maintained for an additional 30minutes to make sure that the unreacted oxide is reduced to a minimum.The resulting product is the ethylene oxide adduct of aphenol-formaldehyde-alkylene polyamine resin in which the ratio of oxideto resin by weight is about 1 to 1.

EXAMPLE II In a manner similar to Example I, a mixed oxide adduct of theresin of Example D was prepared in which the ratio of ethylene oxide topropylene oxide was 1 to 1. The finished product is a material in whichthe ratio of mixed oxides to resin is 6 to 1.

EXAMPLE III In a manner similar to Example I, a mixed oxide adduct ofthe resin of Example D was prepared in which the ratio of ethylene oxideto propylene oxide is l to 2. The finished product contains a ratio of 6parts of mixed oxides to 1 part of resin.

EXAMPLE IV In a manner similar to Example I, 4 pounds of the resin ofExample D and 1 part of sodium hydroxide are charged into a 5 gallonautoclave. These materials are heated to 145 C., and 36 pounds ofpropylene oxide are added over a period of approximately 8 hours attemperatures in the range of 145-150 C. and pressures in the range of6080 p.s.i. After the addition of the propylene oxide was completed, thematerial was further heated for a period of 2 hours so that residualpropylene 7 oxide is reduced to a minimum. The finished product is apropylene oxide adduct of the phenol-formaldehydepolyamine resin inwhich the ratio of propylene oxide to resin is 9 to 1.

EXAMPLE V EXAMPLE VI In an autoclave having a 2-liter capacity, equippedwith a means of external heating, internal cooling coils and mechanicalagitation, there is charged 400 parts of the resin of Example B and 1part sodium hydroxide. Into a transfer bomb there is introduced 605parts ethylene oxide. The resin intermediate is heated to 140 C., andethylene oxide is charged into the reactor until reactor pressure is 80p.s.i. The reaction mixture is gradually heated until an exothermicreaction begins to take place. The external heating is then removed, andethylene oxide is added at such a rate that the temperature ismaintained between 150160 C. with a pressure range of 80-100 p.s.i.After approximately 3 hours all of the oxide has been added to theautoclave, and temperature is maintained for an additional 30 minutes tomake cer tain that the unreacted oxide is reduced to a minimum. Theresulting product is the ethylene oxide adduct of aphenol-formaldehyde-polyamine resin in which the ratio of oxide to resinis 3 to 2 by weight.

EXAMPLE VII In a manner similar to Example VI, 504 parts of the resin ofExample A and 515 parts of ethylene oxide are reacted. The finishedproduct is the ethylene oxide adduct of a phenol-formaldehyde-polyamineresin in which the ratio of oxide to resin is 1 to 1 by weight.

EXAMPLE VIII In a manner similar to Example VI, 600 parts of the resinof Example E was reacted with 400 parts of ethylene oxide which gives afinished product in which the ratio of oxide to resin is 2 to 3 byweight. The oxyalkylation catalyst used in this preparation waspotassium hydroxide.

EXAMPLE IX In an autoclave having a two-liter capacity, equipped with ameans of external heating, internal cooling coils and mechanicalagitation, there is charged 400 parts of the resin of Example E and 2parts sodium hydroxide. Into a transfer bomb there is introduced 300parts of ethylene oxide and 900 parts propylene oxide. The resin isheated to 145 C., and the mixed oxides are charged into the reactoruntil reactor pressure is 60 p.s.i. The reaction mixture is graduallyheated until an exothermic reaction begins to take place. The externalheating is then removed, and the mixed oxides are added at such a ratethat the temperature is maintained between 145- 150 C. with a pressurerange of 80-100 p.s.i. After approximately 4 hours all of the oxide hasbeen added to the autoclave, and the temperature is maintained for anadditional 2 hours to make certain that the unreacted oxide is reducedto a minimum. The resulting product is the mixed oxide adduct of aphenol-formaldehyde-polyamine resin in which the ratio of mixed oxidesto resin is 3 to 1 by weight.

EXAMPLE X In an autoclave having a two-liter capacity, equipped withmeans of external heating, internal cooling coils and mechanicalagitation, there is charged 700 parts of the resin of Example F and 2parts potassium hydroxide. Into a transfer bomb there is introduced 700parts propylene oxide. The intermediate is heated to C., and thepropylene oxide is charged into the react-or until reactor pressure is50 p.s.i. The reaction mixture is gradually heated until an exothermicreaction begins to take place. The external heating is then removed, andpropylene oxide is then added at such a rate that the temperature ismaintained between 135-145" C. with a pressure range of 60-80 p.s.i.After approximately 6 hours all of the propylene oxide has been added tothe autoclave, and the temperature is maintained for an additional 2hours to make certain that the unreacted propylene oxide is reduced to aminimum. The resulting product is the propylene oxide adduct of aphenolformald'ehyde-polyamine resin in which the ratio of oxide to resinis 1 to 1 by weight.

EXAMPLE XI Four hundred fifty parts of the finished product of Example Xis charged into a two-liter autoclave, and 50 parts ethylene oxide areadded at temperatures between 160 C. After the oxide has been added theautoclave is further heated until a constant pressure value is observed.The resulting product is a sequential propylene oxide-ethylene oxideadduct of a phenol-formaldehydepolyamine resin in which there is 10% ofethylene oxide by weight.

EXAMPLE XII In a manner similar to Example I, an ethylene oxide adductof a resin of Example C was prepared in which the ratio of oxide toresin is 2 to 3 by Weight.

The oxyalkylated phenol-formald'ehyde-alkylene polyamine resins of theforegoing examples are made into finished products suitable for use asemulsion-breaking chemicals by blending the resins with about an equalamount by weight of a suitable hydrocarbon vehicle.

Among the suitable hydrocarbon vehicles which can be employed asdiluents is sulfur dioxide extract. This material is a by-product fromthe Ed'eleanu process of refining petroleum in which the undesirablefractions are removed by extraction with liquid sulfur dioxide. Afterremoval of the sulfur dioxide a mixture of hydrocarbons, substantiallyaromatic in character, remains and is designated in the trade as sulfurdioxide extract of S0 extract. Examples of other suitable hydrocarbonvehicles are toluene, xylene, gas oil, diesel fuel, bunker fuel and coaltar solvents. The above cited examples of solvents are adaptable toazeotropic distillation as would also be any other solvent which isimmiscible with water, rniscible with the reacting means and has aboiling point or boiling range in excess of the boiling point of water.

Deemulsification of water-z'n-oil emulsions The compositions of thisinvention are surface-active and are particularly suitable for thedeemulsification of naturally-occurring crude oil emulsions andemulsions resulting from the afore-described desalting processes.Deemulsification is achieved by mixing the deemulsifying agents of thisinvention, at a ratio in the approximate range of one part of thedeemulsifying agent to 2,000- 50,000 parts of the emulsion, andthereafter allowing the emulsion to remain in a relatively quiescentstate during which separation of the oil and water occurs. Withnaturally-occurring emulsions, the temperature of the emulsion may be50-210 R, although temperatures of at least 120 F. are often preferredto accelerate separation of the de'emulsified water and oil phases. Thedeemulsifying agents of this invention may be used in conjunction withother deemulsifying agents from classes such as the petroleum sulfonatetype, of which naphthalene sulfonic acid is an example, the modifiedfatty acid type, and others.

The effectiveness of the compositions of this invention as deemulsifyingagents is illustrated in the following tests and data.

Bottle testing of crude oil emulsions The bottle testing of crude oilemulsions is conducted according to the following procedure: Freshsamples of the emulsion-breaking chemicals in organic solvent solutionare prepared in 10% solutions. These solutions are made by accuratelydiluting 10 milliliters of the emulsion-breaking chemicals in 90milliliters of a mixture of equal parts of anhydros isopropyl alcoholand an aromatic hydrocarbon such as xylene. The mixture is agitated welluntil the emulsion-breaking chemical is completely dissolved.

Theequipment for running the crude oil emulsionbreaking test, inaddition to the foregoing 10% solutions, includes a set of six ouncegraduated prescription bottles, a funnel, a graduated 0.2 milliliterpipette, a thief pipette, a centrifuge, centrifuge tubes and athermometer. The graduated prescription bottles are filled to the 100milliliter mark with the crude oil emulsion to be tested, preferably asample which has been recently collected. If there is any free water inthe crude oil emulsion sample collected, it is bled off before thebottles are filled. Each bottle is inverted several times with the thumbover the opening of each bottle so that the bottle will be coated withan emulsion film.

By means of the 0.2 milliliter pipette, the prescribed volume of the 10%solution of the emulsion-breaking chemical is added to the emulsion inthe bottles. The bottles are then capped and given manual agitation fora predetermined number of counts. The number of counts are determined bya survey of the agitation which can be secured in the system in whichthe crude oil emulsion is being used. If the emulsion requires heat fortreatment, the bottles are placed in hot water bath, the length of timeand temperature determined by the particular plant equipment andpractice in which the particular emulsion is employed. If the plantprovides for hot agitation of the emulsion the bottles may be given acorresponding amount of manual hot agitation.

The bottles are then removed from the hot water bath and the water drop,presence of the bottom settlings (B.S.) layer and color and generalappearance of the oil are noted.

A thief grind-out is taken on all bottles which appear to be promising.A thief grind-out is made by preparing centrifuge tubes filled withgasoline to the 50% mark. The thief pipette is set to the proper lengthby adjusting the rubber stopper so that the bottom of the pipette isabout A inch above the oil-water level of the bottle with maximum waterdrop. This same setting is used for all subsequent thiefings onremaining bottles. The thiefed oil from each bottle is added to thecentrifuge tube to the 100% mark, and the tube is shaken. The samplesare then centrifuged for three minutes.

With certain paraffin base oils a portion of the paraffin is thrown downwith the B.S. If the centrifuge tubes are heated to 150 F. the paraffinwill melt and be dissolved in the gasoline-oil mixture and usually willnot be thrown down again with the B.S. upon centrifuging while hot.However, occasionally the paraflin will re-congeal as the tube coolsduring centrifuging. If this occurs, the tube is removed from thecentrifuge and heated to 150 F. Without shaking or disturbing thesettled B.S. layer. The heated sample is then centrifuged for seconds.This should give a true B.S. reading free of paraffin.

An excess chemical grind-out is then run on each centrifuge tube byadding several drops of a solution in white gasoline or other solvent ofa chemical which causes complete separation of the water and oil. Withsome sensitive emulsions the chemical will cause reemulsification. Inthese instances it is necessary to rethief and add a lesser amount. Eachtube is vigorously shaken .10 to make sure that the packed B.S. layer isbroken up and the tubes heated to F. in the case of troublesome parafiinbase crude oil. The samples are then centrifuged for three minutes.

During the test the speed of the water drop is observed carefully afterthe emulsion-breaking chemical is added to the prescription bottles. Theobservation of the color and brilliance of the oil in transmitted lightis very important. In general, the brilliance and depth of colorincreases with a decrease in B.S. & W. (bottom settlings and water)content. The observations of color are made in the oil in theprescription bottle before and after heat treatment. In the idealtreatment of crude oil emulsions the oil-water line could be a sharp,clean line without any web or sludge present. Presence of a considerableamount of sludge or web is undesirable because this foreign materialwill eventually go to stock in the treating plant and be reported asB.S. Traces of web or sludge, however, will disappear or be removed inthe normal treating plant.

In almost all instances the thief grind-out and excess chemicalgrind-out readings indicate the formula that has most nearly producedcrude oil free from B.S. and water. The most eflicient emulsion-breakingchemical is determined by the foregoing test procedure by the overallconsideration of the following factors: relative speed of the breakingof the emulsion which is usually indicated by speed of water drop, colorand brilliance of the oil layer, the relative absence of web or sludgeat oil-water line and the ability to most nearly produce treated oilthat is free from B.S. and water.

By way of illustrating the effectiveness of the emulsionbreakingchemicals contemplated by this invention, the composition of Example VIand a composition similar to that of Example VI but having a ratio ofethylene oxide to resin of 1:1, identified in the following table asComposition A and Composition B, respectively, were tested as solutionsof between 4 and 5 percent of active ingredient according to theforegoing bottle-testing procedure on samples of 27 gravity crude oilobtained from South Mountain Field, California. The crude oil emulsioncontained about eight percent water. The solutions were added at a ratioof 0.08 part of a 10% solution, as described in the foregoing procedure,to 100 parts of emulsion fluid. The samples were given 200 shakes coldand 100 shakes hot, the hot temperature being F. The observations madeduring the tests were recorded and are summarized in the followingtable.

1 Before hot agitation. 2 After hot agitation.

The composition of Example VII has been found to be effective indesalting operations.

It is to be noted that in the deemulsifying agent of this inventionwherein ethylene oxide is employed as the oxyalkylating agent, theweight ratio of ethylene oxide to resin is at the lower end of the rangeheretofore described and preferably does not exceed a ratio of about2:1. At higher ratios, these compounds are too hydrophilic to be used asemulsion-breaking chemicals.

The invention is hereby claimed as follows:

1. An oxyalkylated alkyl phenol-formalde'hyde-alkylene polyamine resinproduced by heating a mixture of (A) an alkyl phenol selected from thegroup consisting of an ortho and para monoalkyl phenol having a 4-15carbon alkyl group, mixtures of said monoalkyl phenols, and mixtures ofsaid monoalkyl phenol with up to 25% of o, p-dialkyl phenols with 4-15carbons in the alkyl groups; (B) formaldehyde and (C) alkylene polyaminehaving two primary amino groups and alkylene groups of 26 carbons in amole ratio of (A) to (C) of about 1:1 to 10:1, respectively, and a molratio of (B) to the total mols of (A) and (C) of about 0.911 to 15:1,respectively, removing by distillation during said heating water ofreaction of the polycondensation reaction to produce an alkylphenol-formaldehyde-alkylene polyamine resin characterized by alkylenepolyamine units connected in the polycondensate chain by methylenegroups on two amino nitrogens; and oxyalkylating said resin withalkylene oxide selected from the group consisting of ethylene oxide,1,2- propylene oxide and both ethylene oxide and 1,2-propylene oxide inan amount of the latter suflicient to provide in the oxyalkylated alkylphenol-formaldehyde-alkylene polyamine resin a weight ratio ofoxyalkylene groups to said alkyl phenol-formaldehyde-alkylene polyamineresin in the range of about 2:3 to 10:1, respectively.

2. An oxyalkylated alkyl phenol-formaldehyde-alkylene polyamine resinproduced by first heating a mixture of formaldehyde and an alkyl phenolselected from the group consisting of an ortho and para monoalkyl phenolhaving a 4-15 carbon alkyl group, mixtures of said monoalkyl phenols,and mixtures of said monoalkyl phenol with up to 25% of o, p-dialkylphenols with 415 carbons in the alkyl groups to produce a precursoralkyl phenolformaldehyde intermediate condensate, further condensingsaid intermediate condensate by heating it with additional alkyl phenolas aforedefined and formaldehyde and also alkylene polyamine having twoprimary amino groups and alkylene groups of 2-6 carbons, the totalamounts of said alkyl phenol used in both of the aforesaid reactions tosaid alkylene polyamine used in the latter reaction 'being about 1:1 to10:1, respectively, and the total mols of formaldehyde used in both ofthe aforesaid reactions to the total mols of both of said alkyl phenolused in both of the aforesaid reactions and the alkylene polyamine usedin the latter reaction being about 0.9:1 to 1.5 :1, respectively, andremoving 'by distillation during said heating in both of the aforesaidreactions the water of reaction to produce alkylphenol-formaldehyde-alkylene polyamine resin characterized by alkylenepolyamine units connected in the polycondensate chain by methylenegroups on two amino nitrogens; and oxyalkylating said resin withalkylene oxide selected from the group consisting of ethylene .12 oxide,1,2-propylene oxide and both ethylene oxide and 1,2-propylene oxide inan amount of the latter sufiicient to provide in the oxyalkylated alkylphenolformaldehydealkylene polyamine resin a weight ratio of oxyalkylenegroups to said alkyl phenol-formaldehyde-alkylene polyamine resin in therange of about 2:3 to 10: 1, respectively.

3. A polyoxyalkylated resin as claimed in claim 1 wherein the alkyleneoxide employed for said polyoxyalkylation consists of ethylene oxide,and the weight ratio of oxyethylene groups to said alkylphenol-formaldehydealkylene polyamine resin being in the range of about2:3 to 2: 1.

4. A polyoxyalkylated resin as claimed in claim 1 wherein the alkyleneoxide employed for said polyoxyalkylation consists 'of 1,2-propyleneoxide.

5. A polyoxyalkylated resin as claimed in claim 2 wherein the alkyleneoxide employed for said polyoxyalkylation consists of ethylene oxide,and the weight ratio of oxyethylene groups to said alkylphenol-formaldehydealkylene polyamine resin being in the range of about2:3 to 2:1.

6. A polyoxyalkylated resin as claimed in claim 2 wherein the alkyleneoxide employed for said polyoxy References Cited by the Examiner UNITEDSTATES PATENTS 2,839,502 6/1958 De Groote 260-58 2,854,433 9/1958 DeGroote 260-51.5

FOREIGN PATENTS 579,342 9/ 1959 Belgium. 886,766 1/ 1962 Great Britain.

SAMUEL H. BLECH, Primary Examiner.

WILLIAM H. SHORT, Examiner.

H. E. SCHAIN, Assistant Examiner.

2. AN OXYALKYLATED ALKYL PHENOL-FORMALDEHYDE-ALKYLENE POLYAMINE RESINPRODUCED BY FIRST HEATING A MIXTURE OF FORMALDEHYDE AND AN ALKYL PHENOLSELECTED FROM THE GROUP CONSISTING OF AN ORTHO AND PARA MONOALKYL PHENOLHAVING A 4-15 CARBON ALKYL GROUP, MIXTURES OF SAID MONOALKYL PHENOLS,AND MIXTURES OF SAID MONOALKYL PHENOL WITH UP TO 25% OF O, P-DIALKYLPHENOLS WITH 4-15 CARBONS IN THE ALKYL GROUPS TO PRODUCE A PRECURSORALKYL PHENOLFORMALDEHYDE INTERMEDIATE CONDENSATE, FURTHER CONDENSINGSAID INTERMEDIATE CONDENSATE BY HEATING IT WITH ADDITIONAL ALKYL PHENOLAS AFOREDEFINED AND FORMALDEHYDE AND ALSO ALKYLENE POLYAMINE HAVING TWOPRIMARY AMINO GROUPS AND ALKYLENE GROUPS OF 2-6 CARBONS, THE TOTALAMOOUNTS OF SAID ALKYL PHENOL USED IN BOTH OF THE AFORESAID REACTIONS TOSAID ALKYLENE POLYAMINE USED IN THE LATTER REACTION BEING, ABOUT 1:1 TO10:1, RESPECTIVELY, AND THE TOTAL MOLS OF FORMALDEHYDE USED IN BOTH OFTHE AFORESAID REACTIONS TO THE TOTAL MOLS OF BOTH OF SAID ALKY PHENOLUSED IN BOTH OF THE AFORESAID REACTIONS AND THE ALKYLENE POLYAMINE USEDIN THE LATTER REACTION BEING ABOUT 0.9:1 TO 1.5:1, RESPECTIVELY, ANDREMOVING BY DISTILLATION DURING SAID HEATING IN BOTH OF THE AFORESAIDREACTIONS THE WATER OF REACTION TO PRODUCE ALKYLPHENOL-FORMALDEHYDE-ALKYLENE POLYAMINE RESIN CHARACTERIZED BY ALKYLENEPOLYAMINE UNITS CONNECTED IN THE POLYCONDENSATE CHAIN BY METHYLENEGROUPS ON TWO AMINO NITROGENS; AND OXYALKYLATING SAID RESIN WITHALKYLENE OXIDE SELECTED FROM THE GROUP CONSISTING OF ETHYLENE OXIDE,1,2-PROPYLENE OXIDE AND BOTH ETHYLENE OXIDE AND 1,2-PROPYLENE OXIDE INAN AMOUNT OF THE LATTER SUFFICIENT TO PROVIDE IN THE OXYALKYLATED ALKYLPHENOL-FORMALDEHYDEALKYLENE POLYAMINE RESIN A WEIGHT RATIO OFOXYALKYLENE GROUPS TO SAID ALKYL PHENOL-FORMALDEHYDE-ALKYLENE POLYAMINERESIN IN THE RANGE OF ABOUT 2:3 TO 10:1, RESPECTIVELY.